Force-velocity relation and density profiles for biased diffusion in an adsorbed monolayer

In this paper, which completes our earlier short publication [Phys. Rev. Lett. 84, 511 (2000)], we study dynamics of a hard-core tracer particle (TP) performing a biased random walk in an adsorbed monolayer, composed of mobile hard-core particles undergoing continuous exchanges with a vapor phase. In terms of an approximate approach, based on the decoupling of the third-order correlation functions, we obtain the density profiles of the monolayer particles around the TP and derive the force-velocity relation, determining the TP terminal velocity, V_{tr}, as the function of the magnitude of external bias and other system's parameters. Asymptotic forms of the monolayer particles density profiles at large separations from the TP, and behavior of V_{tr} in the limit of small external bias are found explicitly.Comment: Latex, 31 pages, 3 figure

Electrochemical and Photoelectrochemical Investigation of Water Oxidation with Hematite Electrodes

Atomic layer deposition (ALD) was utilized to deposit uniform thin films of hematite (α-Fe2O3) on transparent conductive substrates for photocatalytic water oxidation studies. Comparison of the oxidation of water to the oxidation of a fast redox shuttle allowed for new insight in determining the rate limiting processes of water oxidation at hematite electrodes. It was found that an additional overpotential is needed to initiate water oxidation compared to the fast redox shuttle. A combination of electrochemical impedance spectroscopy, photoelectrochemical and electrochemical measurements were employed to determine the cause of the additional overpotential. It was found that photogenerated holes initially oxidize the electrode surface under water oxidation conditions, which is attributed to the first step in water oxidation. A critical number of these surface intermediates need to be generated in order for the subsequent hole-transfer steps to proceed. At higher applied potentials, the behavior of the electrode is virtually identical while oxidizing either water or the fast redox shuttle; the slight discrepancy is attributed to a shift in potential associated with Fermi level pinning by the surface states in the absence of a redox shuttle. A water oxidation mechanism is proposed to interpret these results

Demonstartion of density dependence of x-ray flux in a laser-driven hohlraum

Experiments have been conducted using laser-driven cylindrical hohlraums whose walls are machined from Ta{sub 2}O{sub 5} foams of 100 mg/cc and 4 g/cc densities. Measurements of the radiation temperature demonstrate that the lower density walls produce higher radiation temperatures than the high density walls. This is the first experimental demonstration of the prediction that this would occur [M. D. Rosen and J. H. Hammer, Phys. Rev. E 72, 056403 (2005)]. For high density walls, the radiation front propagates subsonically, and part of the absorbed energy is wasted by the flow kinetic energy. For the lower wall density, the front velocity is supersonic and can devote almost all of the absorbed energy to heating the wall

Peasants' Choices? Indian Agriculture and the Limits of Commercialization in Nineteenth-Century Bihar

The article attempts to distinguish and locate choices in agricultural production, with special reference to Bihar, India, during the nineteenth century. On the one hand, it considers closely managed and extensively irrigated areas, long involved in trade under the overall control of 'landlords', and, on the other hand, the expanding production of opium, and also of indigo and sugar (so-called 'forced' commercialization), identifying common features and continuities of production and marketing. Particular the importance of advance payments and local intermediaries is stressed. Thus, in contrast with the more usual evolutionary models, based on unitary categories and modes, the essay illustrates ecological, customary, collective, and local political constraints upon agricultural decisions; and this leads to the identification in turn of their different kinds and levels

Reaction Pathways for Oxygen Evolution Promoted by Cobalt Catalyst

The in-depth understanding of the molecular mechanisms regulating the water oxidation catalysis is of key relevance for the rationalization and the design of efficient oxygen evolution catalysts based on earth-abundant transition metals. Performing ab initio DFT+U molecular dynamics calculations of cluster models in explicit water solution, we provide insight into the pathways for oxygen evolution of a cobalt-based catalyst (CoCat). The fast motion of protons at the CoCat/water interface and the occurrence of cubane-like Co-oxo units at the catalyst boundaries are the keys to unlock the fast formation of O\u2013O bonds. Along the resulting pathways, we identified the formation of Co(IV)-oxyl species as the driving ingredient for the activation of the catalytic mechanism, followed by their geminal coupling with O atoms coordinated by the same Co. Concurrent nucleophilic attack of water molecules coming directly from the water solution is discouraged by high activation barriers. The achieved results suggest also interesting similarities between the CoCat and the Mn4Ca-oxo oxygen evolving complex of photosystem II